TW202015648A - Oil-in-water type emulsion composition and production method therefor - Google Patents

Abstract

Provided is an oil-in-water type emulsion composition that exhibits high emulsion stability even when containing an organic acid, a salt thereof, or a derivative thereof. This oil-in-water type emulsion composition contains: a dispersion medium containing water, and an organic acid, a salt thereof, or a derivative thereof; and oil droplets dispersed within the dispersion medium. These oil droplets have a mean particle size of 100 nm or less, and contain an ionic surfactant, a non-ionic surfactant, a higher alcohol, and an oil component. In addition, the ionic surfactant, the non-ionic surfactant, and the higher alcohol form an interface film for the oil droplets.

Description

Oil-in-water emulsified composition and its manufacturing method

The present invention relates to an oil-in-water emulsion composition.

In recent years, cosmetics having high functional characteristics such as whitening effect and antioxidant effect have been desired. In the oil-in-water emulsified composition used in such cosmetics, in order to express high functional properties, adjust pH, etc., most of the organic acids and ascorbic acid, 4-methoxysalicylic acid and the like are mixed in the aqueous phase. Its salt and other electrolytes are used as salt-type drugs.

Patent Document 1 discloses an oil-in-water emulsified composition containing a salt-type agent, a hydrophilic nonionic surfactant, an N-long-chain acyl acidic amino acid monosalt, two or more types of higher fatty acids, and constituent higher fatty acids Soap base, higher alcohol, oil, and water, and emulsified particles are refined by high-pressure emulsification. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-126705

[Problems to be solved by the invention]

For an oil-in-water emulsion composition, if an electrolyte such as organic acid and its salt is blended, there is a problem that the emulsion stability of the emulsion composition decreases.

Therefore, the subject of the present invention is to provide an oil-in-water emulsified composition that exhibits high emulsification stability even if it contains organic acids or salts or derivatives thereof. [Technical means to solve the problem]

<Form 1> An oil-in-water emulsified composition comprising water and a dispersion medium including an organic acid or its salt or its derivative, and Oil droplets dispersed in the above dispersion medium, and The above oil droplets have an average particle size of 100 nm or less, and include ionic surfactants, nonionic surfactants, higher alcohols and oils; The ionic surfactant, the nonionic surfactant and the higher alcohol form an interface film of the oil droplets. <Form 2> The composition according to aspect 1, wherein the organic acid is at least one of alkoxysalicylic acid, L-ascorbic acid, kojic acid, carnosine, tranexamic acid, glycyrrhizic acid, and 1-piperidine propionic acid. <Form 3> The composition according to aspect 1 or 2, wherein the above-mentioned ionic surfactant is a sulfonate type anionic surfactant. <Form 4> The composition of aspect 3, wherein the sulfonate-type anionic surfactant is N-acyl methyl taurine. <Form 5> The composition according to any one of aspects 1 to 4, wherein the nonionic surfactant has an HLB (Hydrophile Lipophile Balance, hydrophilic/oil ratio) of 15.0 or more. <Form 6> The composition according to any one of aspects 1 to 5, wherein the nonionic surfactant is a polyoxyethylene alkyl ether. <Form 7> The composition of aspect 6 wherein the average addition mole number of the polyoxyethylene group in the polyoxyethylene alkyl ether is 20 or more. <Form 8> The composition according to any one of aspects 1 to 7, wherein the higher alcohol has a linear saturated alkyl group having 18 or more carbon atoms. <Form 9> The composition according to any one of aspects 1 to 8, wherein the A/S ratio exceeds 0 and is 3.0 or less. <Form 10> The composition according to any one of aspects 1 to 9, which contains 2 mmol to 30 mmol of the above-mentioned organic acid or salt or derivative thereof with respect to 100 g of the composition. <Form 11> The composition according to any one of aspects 1 to 10 has an L value of 50 or more. <Form 12> A cosmetic base comprising the composition according to any one of claims 1 to 11. <Form 13> A method for manufacturing a composition according to any one of aspects 1 to 11, which is Prepare a mixed liquid containing water, ionic surfactant, nonionic surfactant, higher alcohol and oil, Emulsify the mixed liquid under high pressure at a pressure of 50 MPa or more to prepare an emulsified product, and Organic acid or its salt or its derivative is blended in the emulsion. [Effect of invention]

The present invention can provide an oil-in-water emulsified composition that exhibits high emulsification stability even if it contains an organic acid or its salt or its derivative.

Hereinafter, the embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the invention.

The oil-in-water emulsified composition of the present invention comprises water, a dispersion medium including an organic acid or its salt or its derivative, and oil droplets dispersed in the dispersion medium, and the oil droplets have an average particle diameter of 100 nm or less The composition includes an ionic surfactant, a nonionic surfactant, a higher alcohol and an oil, and an ionic surfactant, a nonionic surfactant and a higher alcohol to form an oil droplet interface film.

With the oil-in-water emulsion composition of the present invention, the emulsion stability can be improved.

It is considered that the action principle of the oil-in-water emulsion composition of the present invention exhibiting high emulsification stability even if it contains an organic acid or its salt or its derivative is as follows, and is not limited by the principle.

For example, it is considered to be a solution obtained by adding a solution of a higher alcohol and oil by heating to a solution of mixed ionic surfactant and water, and emulsifying it at high pressure using a high-pressure homogenizer to form an oil-drop type emulsified combination in water. In the case of substances, an interface film containing an ionic surfactant and a higher alcohol is formed at the interface of dispersed oil droplets. Moreover, by the electrostatic repulsion based on the ionic surfactant in the interface film, the oil droplets can be dispersed relatively stably in water.

However, it is considered that if electrolytes such as organic acids and salts are added to this composition, the electrostatic repulsion effect is weakened due to the electrostatic shielding effect of the electrolyte, which promotes the aggregation and unification of oil droplets, so the oil-in-water emulsion composition The emulsion stability is reduced. In addition, it is considered that the higher alcohol contained in the interface film is easy to crystallize due to lipophilicity, so it is easy to further agglomerate the oil droplets whose electrostatic repulsion has weakened, making the emulsified composition unstable. As a result, the interface film has been crystallized. Higher alcohols tend to be precipitated as particles.

On the other hand, it is considered that in the case of the oil-in-water emulsion composition of the present invention, the non-ionic surfactant is also contained in the emulsified solution. Therefore, an interface containing an ionic surfactant is formed at the interface of the dispersed oil droplets. Interface film of nonionic surfactant and higher alcohol. It is believed that the result is that for this oil droplet, in addition to the electrostatic repulsion based on the ionic surfactant, the entropy repulsion based on the nonionic surfactant also plays a role, so even if the electrostatic repulsion is weakened by the electrostatic shielding effect of the electrolyte, the oil The agglomeration and unification of drops are also suppressed by entropy repulsion, thereby improving the emulsion stability of the oil-in-water emulsion composition.

In addition, it is considered that it is in the oil-in-water emulsion composition described in Patent Document 1. Since the nonionic surfactant is formulated as an independent part after emulsification, it is considered that it is not contained in the interface film of the oil droplets. The nonionic surfactant therefore does not exhibit entropy repulsion in the oil droplets.

"Oil-in-water emulsion composition" The oil-in-water emulsified composition of the present invention includes water, a dispersion medium including an organic acid or a salt or a derivative thereof, and oil droplets dispersed in the dispersion medium with an average particle diameter of 100 nm or less.

When the composition is prepared by, for example, a high-pressure emulsification method, not only is the emulsion stability excellent, but also the viscosity is low, and the transparency is also excellent. Therefore, for example, when used as a cosmetic, the color tone can be changed without changing Shows a mellow sense of use. Here, "mellow" refers to a soft and sticky touch when used, which makes people feel moist as if moisture is kept on the skin when applied to the skin.

Regarding viscosity, for example, a B-type viscometer can be used for evaluation. For example, the viscosity of the composition of the present invention measured at 30°C and 60 rpm can be set to 100 mPa·s or less, 75 mPa·s or less, or 50 mPa·s or less, and can also be set to 5 mPa·s or more, 7 mPa·s or more, or 10 mPa·s or more.

In addition, regarding transparency, for example, the L value calculated from a spectrophotometer such as SE7700 (manufactured by Nippon Denshoku Industries Co., Ltd.) can be evaluated. The closer the L value is to 100, the higher the transparency. Immediately after the composition of the present invention is prepared, the L value can be set to 50 or more, 55 or more, or 60 or more, and 90 or 80 or less. In addition, the composition of the present invention is also excellent in transparency in a state corresponding to a high temperature test or a temperature resistance accelerated test stored at 50°C for 4 weeks, and the L value when stored at 50°C for 4 weeks can be compared with immediately after preparation The ratio of the initial L value is set to 35% or more, 50% or more, or 60% or more.

<oil drop> The oil droplets in the oil phase or the dispersed phase in the oil-in-water emulsion composition have an average particle size of 100 nm or less, and contain ionic surfactants, nonionic surfactants, higher alcohols and oils, and also, ionic Surfactants, nonionic surfactants and higher alcohols form an interface film of oil droplets. The interface membrane can be confirmed by, for example, dialysis, ultracentrifugation, or the like.

In the oil-in-water emulsion composition of the present invention, from the viewpoint of transparency, the average particle diameter of the oil droplets as the dispersed phase is preferably 100 nm or less, 90 nm or less, or 80 nm immediately after preparation Below, or below 70 nm. The lower limit of the average particle diameter is not particularly limited, and for example, it may be 5 nm or more, 10 nm or more, or 20 nm or more. The average particle diameter of the oil droplet can be defined as the average value of the diameter of the oil droplet optically measured by a dynamic light scattering method, for example, when the particle shape of the oil droplet is assumed to be spherical.

In addition, the composition of the present invention is also excellent in emulsion stability when stored at 50°C for 4 weeks, and the increase rate of oil droplets in this state can be suppressed to 30% or less, 25% or less, or 20% or less . The increase rate of this oil droplet can be calculated by the following formula 1 according to the initial value of the average particle diameter of the oil droplet and the average particle diameter of the oil droplet after storage at 50°C for 4 weeks: [Number 1] Increase rate of oil droplets (%) = {(value of average particle diameter of oil droplets stored at 50°C for 4 weeks-initial value of average particle diameter of oil droplets) × 100}/(average particle diameter of oil droplets Initial value) …Equation 1

The blending amount of the ionic surfactant in the oil-in-water emulsion composition of the present invention is not limited to the following, from the viewpoint of emulsification stability and transparency accompanied by electrostatic repulsion, for example, relative to the combination The total amount of the substance may be 0.60 mass% or less, 0.55 mass% or less, or 0.50 mass% or less, and may be 0.20 mass% or more, 0.25 mass% or more, or 0.30 mass% or more.

The formulation amount of the nonionic surfactant is not limited to the following. From the viewpoint of emulsification stability and transparency accompanied by entropy repulsion, for example, it can be set to 3.0% by mass relative to the total composition Below, 2.7% by mass or less, or 2.5% by mass or less, and can be set to 1.0% by mass or more, 1.2% by mass or more, or 1.5% by mass or more.

Also, as the ratio of the surfactant defined as the ratio of the molar amount of the ionic surfactant to the total molar amount of the ionic surfactant and the nonionic surfactant, from the viewpoint of emulsion stability, transparency, etc. Specifically, it can be set to 0.30 or more, 0.35 or more, 0.40 or more, 0.45 or more, or 0.50 or more, and can also be set to 0.70 or less, 0.65 or less, or 0.60 or less.

The blending amount of the higher alcohol is not limited to the following, and from the viewpoint of emulsion stability, for example, it can be set to 2.0% by mass or less, 1.5% by mass or less, 1.0% by mass or less relative to the total composition It may be 0.8 mass% or less, and may be 0.4 mass% or more, 0.5 mass% or more, 0.6 mass% or more, or 0.7 mass% or more.

In addition, the A/S ratio defined as the ratio of the molar amount (A) of the higher alcohol to the total molar amount (S) of the ionic surfactant and the nonionic surfactant is emulsification stability and transparency. From the viewpoint of sex and the like, it can be set to more than 0, 0.3 or more, or 0.5 or more, and can also be set to 4.0 or less, 3.5 or less, or 3.0 or less.

It is considered that if the three components constituting the interface film of the oil droplet are prepared in a balance as described above, the interface film becomes easy to change from a planar structure to a curved structure. It is considered that as a result, the oil droplets become easier to spheroidize, thereby further improving the emulsion stability.

(Ionic surfactant) Any ionic surfactant may be used as long as it can form an interface film of oil droplets, and anionic, cationic or amphoteric ionic surfactants can be used. Among them, from the viewpoint of emulsification stability, it is preferable to use an anionic surfactant.

The anionic surfactant is not limited to the following. For example, at least one of a carboxylate type, a sulfonate type, a sulfate ester type, and a phosphate ester type can be used, and among them, it is preferable to use Sulfonate type of electrostatic shielding generated by electrolyte. The form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt, potassium salt, and lithium salt, alkaline earth metal salts such as magnesium salt, calcium salt, ammonium salt, and amino acid salt.

As the sulfonate-type anionic surfactant, for example, N-acyl methyl taurine can be used, and for example, stearic methyl taurate or lauryl methyl taurine can be preferably used. Salt, nutmeg acetyl methyl taurine, coconut oil fatty acid methyl taurine, etc.

(Nonionic surfactant) The nonionic surfactant is not particularly limited as long as it can form an interface film of oil droplets. For example, a hydrophilic nonionic interface activity with an HLB of 15.0 or more, 15.5 or more, or 16.0 or more can be used. Agent. When the hydrophilic nonionic surfactant is used as a cosmetic, it becomes easier for the user to feel a mellow sense of use. Here, the so-called HLB generally indicates the value of the affinity of the surfactant for water and oil, and is a parameter known as a hydrophilic-lipophilic balance. For example, it can be known by the Griffin method. The calculation method can be easily obtained.

The nonionic surfactant is not limited to the following, and specifically, for example, polyoxyethylene alkyl ether, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan can be used Fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives, polyoxyethylene castor oil/hydrogenated castor oil, polyoxyethylene sterol/hydrogenated sterol, polyethylene glycol At least one of fatty acid esters and polyoxyethylene glyceryl isostearate, among which polyoxyethylene alkyl ethers are preferably used.

In addition, examples of the polyoxyethylene alkyl ether include polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene stearyl ether, etc., among which, preferred It is polyoxyethylene behenyl ether and polyoxyethylene stearyl ether. Specifically, for example, POE (15) cetyl ether (HLB15.5), POE (20) cetyl ether (HLB17.0), POE (23) cetyl ether (HLB18.0) ), POE (20) stearyl ether (HLB18.0), POE (21) stearyl ether (HLB value 18.0), POE (15) oleyl ether (HLB16.0), POE (20) oleyl ether (HLB17.0), POE (50) oleyl ether (HLB18.0), POE (20) behenyl ether (HLB16.5), POE (30) behenyl ether (HLB18.0) , POE (10) (C12-15) alkyl ether (HLB15.5), etc., among which, POE (30) behenyl ether is preferred. Examples of commercially available products of this polyoxyethylene alkyl ether include NIKKOL (trademark) BB-30 (manufactured by Nikko Chemicals Co., Ltd.) and the like. Here, the so-called POE means polyoxyethylene, and the value in parentheses following the POE means the average addition mole number of polyoxyethylene in the compound.

The average addition mole number of polyoxyethylene groups in the polyoxyethylene alkyl ether is preferably 20 or more, 21 or more, 25 or more, or 30 or more from the viewpoint of emulsion stability, transparency, and the like.

(Higher alcohol) The higher alcohol may be any one as long as it can form an interface film of oil droplets together with the above-mentioned ionic surfactant and nonionic surfactant, but from the viewpoint of emulsion stability, it is preferably The organic surfactant and the nonionic surfactant together form a solid or α-gel-like interface film at a temperature above normal temperature, for example, a higher alcohol that is solid at normal temperature. Here, the normal temperature means a range of 5°C to 35°C.

As the higher alcohol, for example, those having a carbon chain length of 16 or more can be used. Specific examples include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetearyl alcohol. , Monostearyl glyceryl ether (shark liver alcohol), 2-decyl myristyl alcohol, lanolin alcohol, cholesterol, hexyl dodecanol, isostearyl alcohol, octyl dodecanol, etc. Chain type higher alcohol etc. Among them, from the viewpoint of sense of use, etc., a higher alcohol having a linear saturated alkyl group having 18 or more carbon atoms is preferred, and behenyl alcohol is particularly preferred.

(Oil content) The oil content is not limited to the following. For example, at least one of liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, and synthetic ester oils can be used.

Examples of liquid fats and oils include avocado oil, camellia oil, turtle oil, Australian walnut oil, corn oil, mink oil, olive oil, rapeseed oil, egg butter, sesame oil, peach kernel oil, wheat germ oil, camellia oil, and castor oil Sesame oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, quince oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, etc.

Examples of solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, goat oil, hardened tallow, palm kernel oil, lard, tallow bone oil, wood wax kernel oil, and hardened Oil, butter oil, wood wax, hydrogenated castor oil, etc.

Examples of waxes include beeswax, candela wax, cotton wax, carnauba wax, bayberry wax, insect wax, spermaceti wax, montan wax, bran wax, lanolin, kapok wax, lanolin acetate, and liquid wool Grease, sugarcane wax, isopropyl lanolin fatty acid, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether , Polyethylene glycol lanolin fatty acid, POE hydrogenated lanolin alcohol ether, etc.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, olefin oligomer, and isododecane Alkane, isohexadecane, etc.

Examples of synthetic ester oils include isopropyl myristate, cetyl caprylate, octyldodecanol myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and nutmeg Myristyl acid, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isohexadecyl stearate, isodecyl stearate Hexaester, 12-cholesterol hydroxystearate, ethylene glycol di-2-ethylhexanoate, fatty acid dipentaerythritol ester, monoisostearic acid N-alkyl glycol ester, octyl glycol dicaprylic acid Ester, diisostearyl malate, glyceryl di-2-heptyl undecanoate, bistrimethylolpropane 2-ethylhexanoate, trimethylolpropane triisostearate, Pentaerythritol tetrakis(2-ethylhexanoic acid) ester, tri-2-ethylhexanoic acid glyceride, trioctanoic acid glyceride, glycerol triisopalmitate, trimethylolpropane triisostearate, 2-B Cetyl hexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptyl undecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil, glyceryl acetate, 2-heptyl undecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyl dodecyl ester, di-2-heptyl adipate Undecyl ester, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate Ester, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, etc.

<Water> The water that can be used in the oil-in-water emulsion composition of the present invention is not particularly limited, and water that can be used in cosmetics, quasi-drugs, and the like can be used. For example, purified water, ion-exchanged water, and tap water can be used. The amount of water to be blended is not particularly limited. For example, from the viewpoint of emulsion stability, it is preferably 50 to 95% by mass, and more preferably 70 to 90% by mass relative to the total composition. In addition, water-soluble alcohol and the like may be used together with water to the extent that the influence does not affect the effects of the present invention.

Examples of water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerol monoalkyl ethers, and sugars. Alcohols, monosaccharides, oligosaccharides, polysaccharides and their derivatives, etc. They can be used alone or in combination.

Examples of lower alcohols include ethanol, propanol, isopropanol, isobutanol, and third butanol.

Examples of the polyhydric alcohol include dihydric alcohols (for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, hexanediol, octanediol, etc.); ternary alcohols (for example, glycerin, trimethylol Propane, etc.); tetrahydric alcohols (e.g., pentaerythritol, such as 1,2,6-hexanetriol, etc.); pentavalent alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol, mannitol, etc.) )Wait.

Examples of the polyol polymer include diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, and polyglycerin.

Examples of the binary alcohol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, and ethylene glycol. Mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.

Examples of glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether , Dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol butyl ether, etc.

Examples of glycol ether esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monophenyl ether acetate. , Ethylene glycol diazide, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ether Acid ester, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.

Examples of glycerin monoalkyl ethers include hexanol, saponyl alcohol, and squalanol.

Examples of sugar alcohols include sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, amylolytic sugar reducing alcohol, and the like.

Examples of monosaccharides include three-carbon sugars (e.g., D-glyceraldehyde, dihydroxyacetone, etc.), and four-carbon sugars (e.g., D-erythrose, D-erythrulose, D-threose, erythritol) Sugar alcohols, etc.), five-carbon sugars (for example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L- Xylulose, etc.), six-carbon sugars (for example, D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D- Tagatose, etc.), seven-carbon sugars (e.g., heptanose, heptose, etc.), eight-carbon sugars (e.g., octulose, etc.), deoxy sugars (e.g., 2-deoxy-D-ribose, 6-deoxy- L-galactose, 6-deoxy-L-mannose, etc.), amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.), uronic acid (For example, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.), etc.

Examples of oligosaccharides include sucrose, gentiotriose, umbellose, lactose, psyllium sugar, isocrotyl saccharides, α,α-trehalose, raffinose, rachose, and syringose ( Umbilicin), stachyose mullein sugar, etc.

Examples of the polysaccharides include cellulose, quince seeds, chondroitin sulfate, starch, polygalactose, dermatan sulfate, glycogen, arabinose, acetoheparin sulfate, hyaluronic acid, xanthan gum, keratan sulfate, Chondroitin, Sanxian gum, mucin sulfate, guar gum, dextran, keratin sulfate, locust bean gum, succinyl glycan, kohloleic acid, etc.

Others, for example, solid glycerin; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP·POE-butyl ether; tripolyoxypropylene glyceryl ether; POP-butyl ether; POP-glyceryl ether phosphate; POP·POE-pentane erythritol ether, polyglycerol, etc., polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and other multi-components can also be used Alcohol etc. Here, POP means polyoxypropylene group.

<Organic acid or its salt or its derivative> The organic acid or its salt or its derivative that can be used in the oil-in-water emulsion composition of the present invention may be any, and is not particularly limited. For example, when it is applied to the skin, it can be used to achieve skin texture Effects such as improvement, such as whitening effect.

The so-called organic acid is an organic compound having a carboxyl group and freely generating hydrogen ions. The compound may also contain amino acids or related substances. Specifically, for example, alkoxysalicylic acid, L-ascorbic acid, kojic acid, carnosine, tranexamic acid, glycyrrhizic acid, and 1-piperidine propionic acid, etc. may be mentioned, and these may be used alone or in combination of plural kinds. Among them, from the viewpoint of whitening effect and the like, alkoxysalicylic acid, L-ascorbic acid, kojic acid, and 1-piperidine propionic acid are preferred. In addition, examples of the alkoxysalicylic acid include 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, 5-methoxysalicylic acid, 5-ethoxysalicylic acid, 5-propoxy Based on salicylic acid and the like, 4-methoxysalicylic acid is preferred.

The organic acid may also be in the form of a salt or a derivative, and these may be used alone or in combination. Here, the form of the salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt, potassium salt, and lithium salt, alkaline earth metal salts such as magnesium salt, calcium salt, ammonium salt, and amino acid salt. In addition, the form of the derivative is, for example, a compound obtained by chemically modifying an organic acid, and examples thereof include chemically modified compounds such as hydroxyl groups or carboxyl groups of organic acids.

The blending amount of the organic acid or its salt or its derivative is not particularly limited. From the viewpoint of the expressibility of the effect of the component, emulsification stability, etc., it can be set to 2 mmol or more based on 100 g of the composition. 3 mmol or more, or 4 mmol or more, and can be set to 30 mmol or less, 25 mmol or less, or 20 mmol or less. The composition of the present invention can maintain a stable emulsified state even if it contains a salt-type drug such as an organic acid, so compared with the previous system, the content of the salt-type drug can be increased, thereby further improving the effect produced by the drug .

<Other ingredients> The oil-in-water emulsified composition of the present invention can be appropriately formulated in accordance with the intended use of the composition, etc. within the range that does not affect the effects of the present invention. Examples of various components include additives that can be normally formulated in cosmetics, for example, amphoteric surfactants such as imidazoline-based amphoteric surfactants; cationic surfactants such as alkyl trimethylammonium salts; Anionic surfactant; POE (30) POP (6) decyl tetradecyl ether and other non-ionic surfactants such as POE·POP alkyl ether; powder such as talc; moisturizer such as polyethylene glycol; Water-soluble polymers such as plant-based polymers, starch-based polymers, and ethylene-based polymers; coating agents such as anionic coating agents, cationic coating agents, and nonionic coating agents; and ultraviolet absorbents such as benzoic acid-based ultraviolet absorbents; 1-hydroxyethane-1,1-bisphosphonic acid and other metal ion blocking agents; neutral amino acids, basic amino acids and other amino acids and their salts or derivatives; monoethanolamine and other organic amines; acrylic acid Polymer emulsions such as resin emulsions; polysiloxane elastomers such as polydimethylsiloxane cross-linked polymers; chelating agents; pH adjusters such as lactic acid-sodium lactate; skin nutrients; vitamin A, vitamin C and their derivatives Vitamins such as vitamins; antioxidants such as vitamin E; antioxidants such as phosphoric acid; various extracts such as caffeine and cork; preservatives such as ethyl paraben; anti-inflammatory agents such as glycyrrhizic acid derivatives; placenta extract, Whitening agents such as magnesium ascorbyl phosphate; activators such as royal jelly; blood flow promoters such as undecylammonium nonanoate; anti-seborrheic agents such as sulfur; pigments; pigments; spices, etc.

Regarding various components, depending on their properties, for example, in the case of oil-in-water emulsions, they can be formulated in the oil phase as the continuous phase lipid and/or the oil phase as the dispersed phase. In addition, since the oil-in-water emulsion composition of the present invention is excellent in emulsion stability, it may not contain higher fatty acids, neutralizing agents for neutralizing the higher fatty acids, and higher fatty acid soaps obtained by neutralization.

"Use of oil-in-water emulsion composition" The oil-in-water emulsified composition of the present invention can be made transparent or translucent depending on the application, and can also exhibit a comfortable and mellow feel when applied to the skin. Therefore, the composition of the present invention exhibiting this property can be used, for example, as a base for cosmetics, especially for a cosmetic for skin. Here, the cosmetics that can be applied to the skin may include what is called an external preparation for skin.

The product form of the cosmetics of the present invention is not particularly limited, and examples thereof include facial cosmetics such as lotions, beauty liquids, lotions, and facial masks; cosmetic cosmetics such as compact powders, lipsticks, and eye shadows; sunscreen cosmetics (sunscreen agents) ; Body cosmetics; aromatic cosmetics; skin cleansing products such as makeup removers, shower gels; hair cosmetics such as hair styling lotions, nourishing lotions, conditioners, shampoos, conditioners, hair cosmetics; ointments, etc.

"Manufacturing method of oil-in-water emulsion composition" The oil-in-water emulsified composition of the present invention containing ultrafine oil droplets having an average particle diameter of 100 nm or less can be prepared by a well-known method called agglomeration method or dispersion method, for example.

The so-called coacervation method is a method of preparing colloids that utilizes interface chemical properties. It is a method of changing from a uniformly dissolved state to a supersaturated state by a certain method to make it appear as a dispersed phase. As specific methods, HLB temperature emulsification method, phase inversion emulsification method, non-aqueous emulsification method, D phase emulsification method, liquid crystal emulsification method, etc. are known.

The so-called dispersion method is a method of making the bulk dispersed phase finer by force. Specifically, it is a method of emulsification using the crushing power of an emulsifier. From the viewpoints of transparency and low viscosity, the dispersion method that can be preferably used in the present invention is a dispersion method using high-pressure emulsification as described in Patent No. 3397171. Here, the so-called high-pressure emulsification is to pre-emulsify the water-phase component and the oil-phase component with a homomixer or the like as needed, and to use a high-pressure homogenizer such as Manton Gaulin, French press, and micro-spray homogenizer under high pressure. A method for obtaining an emulsion having fine emulsified particles with high shear force generated.

When the oil-in-water emulsion composition of the present invention is obtained by the high-pressure emulsification method, it is preferable to prepare a mixed liquid containing water, an ionic surfactant, a non-ionic surfactant, a higher alcohol, and an oil, so that The mixed liquid is emulsified under high pressure at a pressure of 50 MPa or more, 80 MPa or more, or 100 MPa or more to prepare an emulsified product. Subsequently, a composition is prepared by blending organic acid or a salt or derivative thereof in the emulsified product. Before emulsifying, prepare a mixed liquid containing water, ionic surfactant, nonionic surfactant, higher alcohol and oil in advance, so that it is easy to contain ionic interface activity in the interface film of the emulsified oil droplet Agents, nonionic surfactants and higher alcohols.

Here, in the preparation of the mixed liquid, water, an ionic surfactant, a nonionic surfactant, a higher alcohol, and an oil may be mixed in one portion, or a preparation containing a nonionic surfactant, a higher alcohol, and an oil may be separately prepared. An oil-soluble solution of oil and a water-soluble solution containing water and an ionic surfactant, and an oil-soluble solution is added to the water-soluble solution to prepare a mixed solution. In addition, in the preparation of the mixed liquid, a heat treatment may be used as appropriate. [Example]

The following examples illustrate the present invention in further detail, but the present invention is not limited thereto. In addition, below, unless otherwise stated, the blending amount is expressed in mass %.

"Examples 1 to 18 and Comparative Examples 1 to 4" Regarding the composition obtained by the formulations and manufacturing methods of Tables 1 to 8 shown below, the L value, the average particle size and particle size distribution of the oil droplets in the composition, and the properties were evaluated.

<Evaluation of composition> The prepared water-in-oil emulsified composition was filled in a sample tube, various evaluations shown below were carried out, and the results are summarized in Tables 1 to 8 and FIG. 1.

Here, the "initial value" in the table means the evaluation result immediately after the composition is manufactured, and the "50°C 4W" means the evaluation result after storing the sample tube in a constant temperature layer of 50°C for 4 weeks. "RT4W" means the evaluation result after storing the sample tube at room temperature for 4 weeks. In addition, the "A/S ratio" means (mole amount of higher alcohol)/(mole amount of nonionic interfacial agent+mole amount of ionic interfacial agent), and the so-called "surfactant ratio" It means (mol amount of ionic interface agent)/(mol amount of non-ionic interface agent+mol amount of ionic interface agent).

(Evaluation of L value) The L value, which is an index of transparency, was evaluated using a spectrophotometer SE7700 (manufactured by Nippon Denshoku Industries Co., Ltd.).

In addition, the emulsion stability over time was evaluated by calculating the ratio of the L value after 4 weeks at 50°C to the initial L value. It is considered that the higher the ratio coefficient value, the more excellent the emulsion stability over time.

(Evaluation of average particle size and particle size distribution) The average particle size and particle size distribution of oil droplets in the composition were measured using Zeta saizer (manufactured by Sysmex).

(Evaluation of the properties of the composition) The composition in the sample tube was visually observed, and its properties were evaluated according to the following criteria. A: No aggregate or gelation was observed in the composition. B: Agglomerates were slightly confirmed through light. C: Agglomerates or gels are clearly recognized in the composition.

<Combined effect of nonionic surfactants> According to Example 1 and Comparative Example 1, the combined effect of the ionic surfactant and the nonionic surfactant was investigated.

[Table 1]

(Example 1) Mix and heat POE(30) behenyl ether as a nonionic surfactant, behenyl alcohol as a higher alcohol, and liquid paraffin and dimethyl polysiloxane as oil to dissolve , Prepare oil-soluble solution. As an ionic surfactant, sodium stearate methyl taurine, glycerin, 1,3-butanediol, dipropylene glycol, and disodium edetate, and a part of the aqueous solvent containing ion-exchanged water Mix and heat to dissolve to prepare a water-soluble solution. Then, after adding an oil-soluble solution to this water-soluble solution and stirring, a high-pressure homogenizer was used to perform high-pressure emulsification at a pressure of 100 MPa to prepare an emulsified product, and it was cooled. Then, the remaining part of the aqueous solvent in which 4-methoxysalicylic acid potassium salt was added and dissolved as a salt-type agent was added to the emulsified product to prepare an oil-in-water emulsified composition.

(Comparative example 1) The composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that no nonionic surfactant was used and behenyl alcohol and stearyl alcohol were used as higher alcohols.

(result) It is clear from the results in Table 1 that the composition of Comparative Example 1 that does not contain a nonionic surfactant is visually confirmed that the agglomerates and the like become unstable in the emulsified state even under the conditions of room temperature for 4 weeks (RT4W). On the other hand, in the composition of Example 1 containing both the nonionic surfactant and the ionic surfactant, almost no aggregates were confirmed, and the emulsion stability was excellent. In addition, regarding transparency, it was also confirmed that the composition of Example 1 was superior to the composition of Comparative Example 1 in either the initial value or after 4 weeks at 50°C (50W at 4W). Therefore, it can be seen that in the case of formulating a salt-type drug, if the interface film of the emulsified oil droplets contains a nonionic surfactant in addition to the ionic surfactant, the emulsion stability of the composition can be improved.

＜A/S ratio effect 1＞ According to Examples 1 to 8, the effect on the A/S ratio by changing the concentration of higher alcohol was studied.

[Table 2]

(Examples 2 to 8) The compositions of Examples 2 to 8 were prepared in the same manner as in Example 1, except that the compounding ratio described in Table 2 was used.

(result) From the results in Table 2, it can be seen that as the value of the A/S ratio becomes smaller, the emulsification stability at 50°C for 4 weeks (50°C 4W) is further improved.

<Influence of A/S ratio 2> According to Examples 9 to 11, the total amount of higher alcohol, nonionic surfactant and ionic surfactant (hereinafter referred to as "AS amount") is set to be constant Study the effect of the A/S ratio of the state. [table 3]

(Examples 9 to 11) The compositions of Examples 9 to 11 were prepared in the same manner as in Example 1, except that the compounding ratio described in Table 3 was used.

(result) From the results in Table 3, it can be seen that when the amount of AS is fixed to about 3% by mass, it is confirmed that the L value is reduced every time the A/S ratio is reduced, and the L value after 4 weeks at 50°C (50°C 4W) is relative to the initial L value The ratio (%) tends to be improved, thereby improving the emulsion stability of the composition.

<Influence ratio of surfactant 1> According to Examples 2, 12, and 13, the effect of the surfactant ratio was investigated.

[Table 4]

(Examples 12 and 13) The compositions of Examples 12 and 13 were prepared in the same manner as Example 1, except that the compounding ratio described in Table 4 was used.

(result) From the results in Table 4, it can be seen that when the A/S ratio is fixed at 0.75, it is confirmed that both the surfactant ratio and the emulsion stability of the composition can be improved.

<Influence ratio of surfactant 2> According to Examples 3, 10, and 14 and Comparative Examples 2 and 3, the influence of the surfactant ratio was studied.

[table 5]

(Example 14) The composition of Example 14 was prepared in the same manner as Example 1 except that the compounding ratio described in Table 5 was used.

(Comparative example 2) The composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that the ionic surfactant was not used and the formulation ratio described in Table 5 was used.

(Comparative example 3) The composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that the nonionic surfactant was not used and the formulation ratio described in Table 5 was used.

(result) From the results in Table 5, in particular, it is equivalent to the results of the L value and properties of the temperature resistance accelerated test after 50 weeks 4 weeks (50 °C 4W), and the ratio of the L value after 50 weeks 4 weeks to the initial L value As a result, it can be seen that if the A/S ratio is fixed to 1 and the surfactant ratio is changed, the compositions of Examples 3, 10, and 14 using both ionic surfactants and nonionic surfactants are confirmed Compared with the compositions of Comparative Examples 2 and 3 using either, the emulsion stability can be improved for a long period of time.

<Influence ratio of surfactant 3> The effect on the ratio of surfactants according to Examples 4, 15 and 16 was studied.

[Table 6]

(Examples 15 and 16) The compositions of Examples 15 and 16 were prepared in the same manner as in Example 1, except that the compounding ratio described in Table 6 was used.

(result) From the results of Table 6, it can be seen that when the A/S ratio is fixed at 1.25, it is confirmed that both the surfactant ratio and the emulsion stability of the composition can be improved.

<Influence ratio of surfactant 4> The effect on the ratio of surfactants according to Examples 5, 17 and 18 was studied.

[Table 7]

(Examples 17 and 18) The compositions of Examples 17 and 18 were prepared in the same manner as Example 1, except that the compounding ratio described in Table 7 was used.

(result) As is clear from the results in Table 7, when the A/S ratio was fixed at 1.5, it was confirmed that both the surfactant ratio and the emulsion stability of the composition can be improved.

<Effect of nonionic surfactants in the oil droplet interface film> According to Example 3 and Comparative Example 4, the influence of the nonionic surfactant in the interface film of oil droplets was studied. In addition, the particle size distribution of the oil droplets in the compositions in Example 3 and Comparative Example 4 after being left at room temperature for 4 weeks (RT4W) is shown in FIG. 1.

[Table 8]

(Comparative example 4) Stearic alcohol, behenyl alcohol, dimethyl polysiloxane, α-olefin oligomer, stearic acid, and behenic acid were stirred and mixed at 80°C to prepare an oil-soluble solution. Part of the ion-exchanged water, sodium N-stearyl-L-glutamate, potassium hydroxide, glycerin, 1,3-butanediol, ethanol and disodium edetate at 70°C Prepare water-soluble solutions. Then, the oil-soluble solution was stirred in the water-soluble solution while mixing, and high-pressure emulsification was carried out using a high-pressure homogenizer at a pressure of 55 MPa to prepare an emulsified product. Then, in a mixed solution in which the remaining part of ion-exchanged water, POE (25) cetyl ether, and potassium 4-methoxysalicylate are dissolved by stirring and mixing, the obtained emulsified product is mixed while stirring, Preparation of oil-in-water emulsion composition. Furthermore, this composition corresponds to the composition of Example 2 in Patent Document 1.

(result) It can be seen from the results in Table 8 that the composition of Comparative Example 4 is inferior to the composition of Example 3 in transparency. It is considered that the reason is that the average particle diameter of the oil droplets is the same even if the degree is the same. From the results in FIG. 1, it is known that the particle size distribution of the oil droplets in the composition is monodispersed in Example 3, and the ratio of coarse oil droplets is Comparative Example 4 is also lower.

Since the composition of Comparative Example 4 uses POE (25) cetyl ether as a nonionic surfactant as an independent component to be formulated after emulsification under high pressure, it is considered that the interface film of oil droplets does not contain nonionic Surfactant. On the other hand, since the composition of Example 3 is a nonionic surfactant mixed with an ionic surfactant and a higher alcohol before high-pressure emulsification, it is considered that the interface film of the oil droplet also contains a nonionic interface Active agent. Therefore, it is believed that this situation causes a difference in the particle size distribution of the oil droplets in the composition, that is, the transparency and emulsification stability of the composition are improved.

"Formulation example of oil-in-water emulsion composition" The formulation examples of cosmetics using the oil-in-water emulsified composition of the present invention as a base are listed below, but are not limited to these examples. In addition, the cosmetic liquid, sunscreen cosmetics, moisturizing gel, and makeup remover cosmetics described in the following formulation examples are excellent in transparency, and have a mellow use feeling based on the oil-in-water emulsion composition of the present invention.

＜Formulation Example 1 Beauty Liquid＞ [Table 9]

(Manufacturing method of beauty liquid) The nonionic surfactants, higher alcohols and oils described in Table 9 are mixed and heated to dissolve to prepare an oil-soluble solution. Then, for ionic surfactants, humectants, pH buffers, preservatives, The chelating agent and ion exchanged water are mixed and heated to dissolve to prepare a water-soluble solution. After adding the oil-soluble solution to the obtained water-soluble solution and stirring, high-pressure emulsification was performed under a pressure of 100 MPa using a high-pressure homogenizer to prepare an emulsified product and cooled. Then, a solution in which potassium 4-methoxysalicylate as a salt-type agent was added and dissolved in ion exchanged water was added to the emulsion to prepare a beauty solution.

<Formulation Example 2 sunscreen cosmetics> [Table 10]

(Manufacturing method of sunscreen cosmetics) The nonionic surfactants, higher alcohols and oils described in Table 10 are mixed and heated to dissolve to prepare an oil-soluble solution. Then, the ionic surfactants, ultraviolet absorbers, humectants, chelating agents, The preservative, pH buffer, stabilizer, and ion exchanged water are mixed and heated to dissolve to prepare a water-soluble solution. After adding the oil-soluble solution to the obtained water-soluble solution and stirring, high-pressure emulsification was performed under a pressure of 100 MPa using a high-pressure homogenizer to prepare an emulsified product and cooled. Then, a solution in which potassium 4-methoxysalicylate as a salt-type agent was added and dissolved in ion exchanged water was added to the emulsified product to prepare a sunscreen cosmetic.

<Formulation Example 3 Moisturizing Gel> [Table 11]

(Manufacturing method of moisturizing gel) The nonionic surfactants, higher alcohols and oils described in Table 11 are mixed and heated to dissolve to prepare an oil-soluble solution. Then, the ionic surfactants, tackifiers, moisturizers, chelating agents, The pH buffer solution and ion-exchange water are mixed and heated to dissolve to prepare a water-soluble solution. After adding the oil-soluble solution to the obtained water-soluble solution and stirring, high-pressure emulsification was performed under a pressure of 100 MPa using a high-pressure homogenizer to prepare an emulsified product and cooled. Then, a solution in which potassium 4-methoxysalicylate as a salt-type agent was added and dissolved in the ion-exchanged water was added to the emulsified product to prepare a moisturizing gel.

<Formulation Example 4 makeup remover> [Table 12]

(Manufacturing method of makeup remover) Mix and dissolve the nonionic surfactants, higher alcohols and oils described in Table 12 by heating to prepare oil-soluble solutions, and then, to the ionic surfactants, alcohols, moisturizers, chelating agents, pH buffers Liquid, stabilizer, and ion-exchange water are mixed and heated to dissolve to prepare a water-soluble solution. After adding the oil-soluble solution to the obtained water-soluble solution and stirring, high-pressure emulsification was performed under a pressure of 100 MPa using a high-pressure homogenizer to prepare an emulsified product and cooled. Then, a solution in which potassium 4-methoxysalicylate as a salt-type agent is added and dissolved in the ion-exchanged water is added to the emulsion to prepare a makeup remover.

Figure 1 is a graph related to the particle size distribution of oil droplets in an oil-in-water emulsion composition.

Claims (13)

An oil-in-water emulsified composition comprising water, a dispersion medium including an organic acid or a salt or a derivative thereof, and oil droplets dispersed in the dispersion medium, and The above oil droplets have an average particle size of 100 nm or less, and include ionic surfactants, nonionic surfactants, higher alcohols and oils; The ionic surfactant, the nonionic surfactant and the higher alcohol form an interface film of the oil droplets. The composition of claim 1, wherein the organic acid is at least one of alkoxysalicylic acid, L-ascorbic acid, kojic acid, carnosine, tranexamic acid, glycyrrhizic acid, and 1-piperidine propionic acid. The composition according to claim 1 or 2, wherein the above-mentioned ionic surfactant is a sulfonate type anionic surfactant. The composition according to claim 3, wherein the sulfonate-type anionic surfactant is N-acetylmethyl taurine. The composition according to any one of claims 1 to 4, wherein the HLB of the nonionic surfactant is 15.0 or more. The composition according to any one of claims 1 to 5, wherein the nonionic surfactant is a polyoxyethylene alkyl ether. The composition according to claim 6, wherein the average addition mole number of the polyoxyethylene group in the polyoxyethylene alkyl ether is 20 or more. The composition according to any one of claims 1 to 7, wherein the higher alcohol has a linear saturated alkyl group having 18 or more carbon atoms. The composition according to any one of claims 1 to 8, wherein the A/S ratio exceeds 0 and is 3.0 or less. The composition according to any one of claims 1 to 9, which contains 2 mmol to 30 mmol of the above-mentioned organic acid or salt or derivative thereof with respect to 100 g of the composition. The composition according to any one of claims 1 to 10 has an L value of 50 or more. A cosmetic base comprising the composition according to any one of claims 1 to 11. A method for manufacturing a composition as claimed in any one of claims 1 to 11, which is Prepare a mixed liquid containing water, ionic surfactant, nonionic surfactant, higher alcohol and oil, Emulsify the mixed liquid at a high pressure under a pressure of 50 MPa or more to prepare an emulsified product, and Organic acid or its salt or its derivative is blended in the emulsion.

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